Catalyst composition for polymerization of olefins

Abstract

A catalyst composition including the compound of Formula I as an internal electron donor, ##STR00001## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are independently selected from a group consisting of hydrogen, straight, branched and cyclic alkyl and aromatic substituted and unsubstituted hydrocarbyl having 1 to 20 carbon atoms; R.sub.7 is selected from a group consisting of straight, branched and cyclic alkyl and aromatic substituted and unsubstituted hydrocarbyl having 1 to 20 carbon atoms; and R.sub.8 is selected from a group consisting of aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms. Also disclosed is a process for preparing said polymerization catalyst composition; a polymerization catalyst system comprising said catalyst composition, a co-catalyst and optionally an external electron donor; a polyolefin obtainable by the process; and use of the compound of Formula I as in internal electron donor in catalysts for polymerization of olefins.

Claims

1. A catalyst composition for the polymerization of olefins, which catalyst composition comprises the compound represented by Formula I as an internal electron donor, ##STR00013## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are the same or different and are independently selected from the group consisting of hydrogen, straight, branched and cyclic alkyl and aromatic substituted and unsubstituted hydrocarbyl having 1 to 20 carbon atoms; R.sub.7 is selected from the group consisting of straight, branched and cyclic alkyl and aromatic substituted and unsubstituted hydrocarbyl having 1 to 20 carbon atoms; and R.sub.8 is selected from the group consisting of aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms; N is nitrogen atom; O is oxygen atom; and C is carbon atom.

2. The catalyst composition according to claim 1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.10 straight and branched alkyl; C.sub.3-C.sub.10 cycloalkyl; C.sub.6-C.sub.10 aryl; and C.sub.7-C.sub.10 alkaryl and aralkyl groups.

3. The catalyst composition according to claim 1, wherein R.sub.1 and R.sub.2 are each a hydrogen atom and R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are independently selected from the group consisting of C.sub.1-C.sub.10 straight and branched alkyl; C.sub.3-C.sub.10 cycloalkyl; C.sub.6-C.sub.10 aryl; and C.sub.7-C.sub.10 alkaryl and aralkyl groups.

4. The catalyst composition according to claim 1, wherein when one of R.sub.3 and R.sub.4 and one of R.sub.5 and R.sub.6 has at least one carbon atom, then the other one of R.sub.3 and R.sub.4 and of R.sub.5 and R.sub.6 is each a hydrogen atom.

5. The catalyst composition according to claim 1, wherein R.sub.7 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, benzyl, substituted benzyl and halophenyl groups.

6. The catalyst composition according to claim 1, wherein R.sub.8 is selected from the group consisting of C.sub.6-C.sub.10 aryl; and C.sub.7-C.sub.10 alkaryl and aralkyl groups.

7. The catalyst composition according claim 1, wherein the internal electron donor is selected from the group consisting of 4-[benzoyl(methyl)amino]pentan-2-yl benzoate; 2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate; 4-[benzoyl (ethyl)amino]pentan-2-yl benzoate and 4-(methylamino)pentan-2-yl bis (4-methoxy)benzoate).

8. A process for preparing the catalyst composition according to claim 1, comprising contacting a magnesium-containing support with a halogen-containing titanium compound and an internal electron donor according to Formula I.

9. The process according to claim 8, which comprises: i) contacting a compound R.sup.9.sub.zMgX.sub.2-z wherein R.sup.9 is aromatic, aliphatic or cyclo-aliphatic group containing 1 to 20 carbon atoms, X is a halide, and z is in a range of larger than 0 and smaller than 2, with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, which is a compound Mg(OR.sup.1).sub.xX.sub.2-x in a solid form, wherein x is in a range of larger than 0 and smaller than 2; ii) contacting the compound Mg(OR.sup.1).sub.xX.sub.2-x in a solid form with at least one activating compound selected from the group consisting of electron donors and compounds of formula M(OR.sup.10).sub.v-w(OR.sup.11).sub.w, wherein M is Ti, Zr, Hf, Al or Si and M(OR.sup.10).sub.v-w(R.sup.11).sub.w, wherein M is Si, each R.sup.10 and R.sup.11, independently, represent an alkyl, alkenyl or aryl group, v is the valency of M, v being either 3 or 4 and w is smaller than v to give a second intermediate reaction product; and iii) contacting the second intermediate reaction product with a halogen-containing Ti-compound, an internal electron donor represented by Formula I, ##STR00014## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are the same or different and are independently selected from the group consisting of hydrogen, straight, branched and cyclic alkyl and aromatic substituted and unsubstituted hydrocarbyl having 1 to 20 carbon atoms; R.sub.7 is selected from the group consisting of straight, branched and cyclic alkyl and aromatic substituted and unsubstituted hydrocarbyl having 1 to 20 carbon atoms; and R.sub.8 is selected from the group consisting of aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms; N is nitrogen atom; O is oxygen atom; and C is carbon atom.

10. A catalyst composition obtained by the process according to claim 8.

11. A polymerization catalyst system comprising the catalyst composition according to claim 1, a co-catalyst and optionally an external electron donor.

12. A process of making a polyolefin, comprising contacting an olefin with the catalyst system according to claim 11.

13. The catalyst composition according to claim 3, wherein R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are independently selected from C.sub.1-C.sub.10 straight and branched alkyl and phenyl.

14. The catalyst composition according to claim 6, wherein R.sub.8 is selected from the group consisting of substituted or unsubstituted phenyl, benzyl, naphthyl, ortho-tolyl, para-tolyl or anisol groups.

15. The process according to claim 9, wherein the first intermediate reaction product is contacted with an alcohol and a titanium tetraalkoxide in step ii).

16. A polymerization catalyst system comprising the catalyst composition according to claim 7, a co-catalyst and optionally an external electron donor.

17. The catalyst composition according to claim 10, wherein R.sub.1 and R.sub.2 are each a hydrogen atom; R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, or phenyl groups; R.sub.7 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, benzyl, substituted benzyl and halophenyl groups; and R.sub.8 is phenyl.

18. A polymerization catalyst system comprising the catalyst composition according to claim 17, a co-catalyst and optionally an external electron donor.

Description

EXAMPLES

Preparation of 4-[benzoyl(methyl)amino]pentan-yl benzoate (AB)

(1) Step a)

(2) ##STR00007##

(3) 40% monomethylamine solution in water (48.5 g, 0.625 mol) was added drop wise to a stirred solution of substituted pentane-2,4-dione (50 g, 0.5 mol) in toluene (150 ml. After the addition, the reaction mass was stirred at room temperature for 3 hours and then refluxed. During the reflux the water formed was azeotropically removed using a Dean-stark trap. Then the solvent was removed under reduced pressure to give 4-(methylamino)pent-3-en-2-one, 53.5 g, which was then directly used for reduction.

(4) Step b)

(5) ##STR00008##

(6) 4-(methylamino)-pent-3-en-2-one (100 g) was added to a stirred mixture of 1000 ml 2-propanol and 300 ml toluene. To this solution, small piece of metallic sodium 132 g was gradually added at a temperature of between 25-60? C. The reaction mass was refluxed for 18 h. The mass was cooled to room temperature and was poured in cold water and extracted with dichloromethane. The extract was dried over sodium sulfate, filtered and then evaporated under reduced pressure to give 65 g 4-(methylamino)pentan-2-ol (isomer mixture)oil.

(7) Step c)

(8) ##STR00009##

(9) 4-(methylamino)pentan-2-ol (10 g) was added to a mixture of pyridine (16.8 g) and toluene (100 ml). The mass was cooled to 10? C. and benzoyl chloride (24 g) was added drop wise. The mixture was refluxed for 6 h. The mixture was then diluted with toluene and water. The organic layer was washed with diluted HCl, water saturated bicarbonate and brine solution. The organic layer was dried over sodium sulfate, filtered and then evaporated under reduced pressure. The residue was purified by flash chromatography to form 25 g product as thick oil. The product was characterized by .sup.1H NMR and .sup.13C NMR: m/z=326.4 (m+1), .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.95-7.91 (m, 1H), 7.66-7.60 (m, 2H), 7.40-7.03 (m, 5H), 6.78-6.76 (m, 2H), 4.74-5.06 (br m, 1H), 3.91-3.82 (m, 1H), 2.83-2.56 (ddd, 3H), 2.02-1.51 (m, 1H), 1.34-1.25 (dd, 1H), 1.13-1.02 (m, 6H); .sup.13C NMR (75 MHz, CDCl.sub.3), ?=170.9, 170.4, 170.3, 164.9, 164.6, 135.9, 135.8, 135.2, 131.8, 131.7, 131.6, 129.6, 129.4, 129.3, 128.9, 128.4, 128.3, 128.2, 128.0, 127.7, 127.3, 127.2, 127.1, 127.0, 125.7, 125.6, 125.0, 124.9, 68.3, 67.5, 67.3, 49.8, 49.4, 44.9, 44.4, 39.7, 39.0, 38.4, 38.3, 30.5, 29.8, 25.5, 25.1, 19.33, 19.1, 18.9, 18.3, 17.0, 16.8, 16.7.

(10) By applying the same method of preparation, internal electron donors as described and characterized in Table 1 were also obtained:

(11) TABLE-US-00001 TABLE 1 Compound Structure 4-[ethyl(phenylcarbonyl)amino]pentan-2-yl benzoate (AB-Et): m/z = 339 (m + 1), .sup.1H NMR (300MHz, CDCl.sub.3) ? = 1-2(m, 9H), 2-2.6(m 4H), 4-4.2 (m, 1H), 5- 5.4(m, 1H), 7-8.2(m, 10H), .sup.13C NMR (75 MHz, CDCl.sub.3), ? = 17.5, 19, 20, 36, 42, 52, 70, 126- 140, 166, 172. 0 2,2,6,6-tetramethyl-5-(N- methylbenzamido)heptan-3-yl-benzoate (AB- TMH): m/z = 409, .sup.1H NMR (300MHz, CDCl.sub.3) ? = 0.94 (d, 2H), 1.2 (d, 9H), 2.6(s, 3H), 4.8(d, 1H), 4.9(d, 1H), 5.1(t, 2H), 7.2-8.2(10H). .sup.13C NMR (75 MHz, CDCl.sub.3), ? = 26-28, 34, 38, 60, 81, 126- 138, 166, 174. 4-(4-methoxy-N-methylbenzamido)pentane-2-yl- 4-methoxy benzoate (AB-p-OMePh) m/z = 385, .sup.1H NMR (300MHz, CDCl.sub.3) ? = 1.1- 1.3(m, 6H), 1.8-1.9(t, 2H), 3.4(s, 3H), 3.8(s, 6H), 4(m, 1H), 4.6(m, 1H), 6.4-7.8(m, 8H). .sup.13C NMR (75 MHz, CDCl.sub.3), ? = 18-22, 28, 32, 40, 46, 52, 56-58, 68, 114, 123, 128-130, 132, 160, 164, 166, 172.

Example 1

(12) Preparation of the Catalyst Composition

(13) A. Grignard Formation Step (Step A)

(14) This step was carried out as described in Example XVI of EP 1 222 214 B1. This Example is incorporated by reference.

(15) A stainless steel reactor of 9 I volume was filled with magnesium powder 360 g. The reactor was brought under nitrogen. The magnesium was heated at 80? C. for 1 hour, after which a mixture of dibutyl ether (1 liter) and chlorobenzene (200 ml) was added. Then iodine (0.5 g) and n-chlorobutane (50 ml) were successively added to the reaction mixture. After the color of the iodine had disappeared, the temperature was raised to 94? C. Then a mixture of dibutyl ether (1.6 liter) and chlorobenzene (400 ml) was slowly added for 1 hour, and then 4 liter of chlorobenzene was slowly added for 2.0 hours. The temperature of reaction mixture was kept in interval 98-105? C. The reaction mixture was stirred for another 6 hours at 97-102? C. Then the stirring and heating were stopped and the solid material was allowed to settle for 48 hours. By decanting the solution above the precipitate, a solution of phenylmagnesiumchloride reaction product A with a concentration of 1.3 mol Mg/I has been obtained. This solution was used in the further catalyst preparation.

(16) B. Preparation of the First Intermediate Reaction Product (Step B)

(17) This step was carried out as described in Example XX of EP 1 222 214 B1 (this Example is incorporated by reference), except that the dosing temperature of the reactor was 35? C., the dosing time was 360 min and the propeller stirrer was used. 250 ml of dibutyl ether was introduced to a 1 liter reactor. The reactor was fitted by propeller stirrer and two baffles. The reactor was thermostated at 35? C. The solution of reaction product of step A (360 ml, 0.468 mol Mg) and 180 ml of a solution of 55 ml of tetraethoxysilane (TES) in 125 ml of dibutyl ether (DBE), were cooled to 10? C., and then were dosed simultaneously to a mixing device of 0.45 ml volume supplied with a stirrer and jacket. Dosing time was 360 min. Thereafter the premixed reaction product A and the TES-solution were introduced to a reactor. The mixing device (mini-mixer) was cooled to 10? C. by means of cold water circulating in the mini-mixer's jacket. The stirring speed in the mini-mixer was 1000 rpm. The stirring speed in reactor was 350 rpm at the beginning of dosing and was gradually increased up to 600 rpm at the end of dosing stage. On the dosing completion the reaction mixture was heated up to 60? C. and kept at this temperature for 1 hour. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting. The solid substance was washed three times using 500 ml of heptane. As a result, a pale yellow solid substance, reaction product B (the solid first intermediate reaction product; the support), was obtained, suspended in 200 ml of heptane. The average particle size of support was 22 ?m and span value (d.sub.90?d.sub.10)/d.sub.50=0.5.

(18) C. Preparation of the Second Intermediate Reaction Product (Step C)

(19) Support activation was carried out as described in Example IV of WO/2007/134851 to obtain the second intermediate reaction product. This Example is incorporated by reference.

(20) In inert nitrogen atmosphere at 20? C. a 250 ml glass flask equipped with a mechanical agitator is filled with slurry of 5 g of reaction product of step B dispersed in 60 ml of heptane. Subsequently a solution of 0.22 ml ethanol (EtOH/Mg=0.1) in 20 ml heptane is dosed under stirring during 1 hour. After keeping the reaction mixture at 20? C. for 30 minutes, a solution of 0.79 ml titanium tetraethoxide (TET/Mg=0.1) in 20 ml of heptane was added for 1 hour. The slurry was slowly allowed to warm up to 30? C. for 90 min and kept at that temperature for another 2 hours. Finally the supernatant liquid is decanted from the solid reaction product (the second intermediate reaction product; activated support) which was washed once with 90 ml of heptane at 30? C.

(21) D. Preparation of the Catalyst Component (Step D)

(22) A reactor was brought under nitrogen and 125 ml of titanium tetrachloride was added to it. The reactor was heated to 100? C. and a suspension, containing about 5.5 g of activated support (step C) in 15 ml of heptane, was added to it under stirring. Then the temperature of reaction mixture was increased to 110? C. for 10 min and 1.92 g of 4-[benzoyl(methyl)amino]pentan-2-yl benzoate (aminobenzoate, AB, AB/Mg molar ratio=0.15) in 3 ml of chlorobenzene was added to reactor and the reaction mixture was kept at 115? C. for 105 min. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which the solid product was washed with chlorobenzene (125 ml) at 100? C. for 20 min. Then the washing solution was removed by decanting, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115? C. for 30 min, after which the solid substance was allowed to settle. The supernatant was removed by decanting, and the last treatment was repeated once again. The solid substance obtained was washed five times using 150 ml of heptane at 60? C., after which the catalyst component, suspended in heptane, was obtained.

(23) Polymerization of Propylene

(24) Polymerization of propylene was carried out in a stainless steel reactor (with a volume of 0.7 l) in heptane (300 ml) at a temperature of 70? C., total pressure 0.7 MPa and hydrogen presence (55 ml) for 1 hour in the presence of a catalyst system comprising the catalyst component according to step D, triethylaluminum (TEAL) as co-catalyst and n-propyltrimethoxysilane (nPTMS) as external donor. The concentration of the catalyst component was 0.033 g/l; the concentration of TEAL was 4.0 mmol/l; the concentration of nPTMS was 0.2 mmol/l. Data on the catalyst performance for the propylene polymerization is presented in Table 2.

Example 2

(25) Example 2 was carried out in the same way as Example 1, but 4-[benzoyl(ethyl)amino]pentan-2-yl benzoate (formula IX, AB-Et, AB-Et/Mg molar ratio=0.15) in step D was used instead of AB.

Example 3

(26) Example 3-1 was carried out in the same way as Example 1, but 4-(methylamino)-pentane-2-ol di(4-methoxybenzoate) (formula XII, AB-p-MeOPh, AB-p-MeOPh/Mg molar ratio=0.15) in step D was used instead of AB.

Example 4

(27) Example 4 was carried out in the same way as Example 1, but 2,2,6,6-tetramethyl-5-(methyl)amino]heptan-3-ol dibenzoate (formula VIII, AB-TMH, AB-TMH/Mg molar ratio=0.15) in step D was used instead of AB.

Example 5

(28) Example 5 was carried out in the same way as Example 1, but 5 g of Mg(OEt).sub.2 (Aldrich grade) as the Mg-containing support and 2.15 g of AB (AB/Mg molar ratio=0.15) were used in step D.

Example 6

(29) Example 6 was carried out in the same way as Example 1, but 5 g of the Mg-containing support prepared according to U.S. Pat. No. 5,077,357 (production method incorporated by reference) and 1.43 g of AB (AB/Mg molar ratio=0.15) were used in step D.

Example CE1 (Comparative Example 1)

(30) Example CE1 was carried out in the same way as Example 1, but di-n-butylphthalate (DBP)(DBP/Mg molar ratio=0.15) was used instead of AB.

Example CE2 (Comparative Example 2)

(31) Example CE2 was carried out in the same way as Example 1, but 4-[benzoylamino]pentan-2-yl benzoate as described in WO2011106494A1 (incorporated by reference) (AB-H, AB-H/Mg molar ratio=0.15) was used instead of AB.

Example CE3 (Comparative Example 3)

(32) Example CE3 was carried out in the same way as Example 5, but 4-[benzoylamino]pentan-2-yl benzoate (AB-H, AB-H/Mg molar ratio=0.15) was used instead of AB.

(33) TABLE-US-00002 TABLE 2 PP ID type ID, Ti, yield, APP, MFR, Ex. (formula) wt. % wt. % kg/g cat. wt. % XS, % dg/min Mw/Mn 1 AB 17.9 2.4 4.4 0.9 2.5 0.6 7.7 (II) 2 AB-Et 15.6 3.0 4.8 1.7 3.6 1.0 7.4 (IX) 3 AB-p-OMePh (XII) 10.8 3.2 4.7 1.6 4.1 2.4 6.2 4 AB-TMH 7.0 2.9 5.6 1.1 5.6 5.7 7.1 (VIII) 5 AB 19.8 4.5 5.5 1.4 2.7 0.9 7.8 (II) 6 AB 20.4 4.3 6.3 0.9 2.5 1.1 7.5 (II) CE1 DBP 10.5 2.6 13.5 0.4 2.7 12.7 4.8 CE2 AB-H.sup.1) 10.0 2.6 5.5 0.7 3.5 4.6 6.5 CE3 AB-H.sup.1) 10.3 2.9 5.7 0.9 3.6 4.2 6.4 .sup.1)NH group instead of NMe group in AB.

(34) The Examples show that a novel catalyst composition for polymerization of olefins was obtained and that said catalyst composition shows better performance, especially shows better control of stereochemistry and allows preparation of polyolefins having a broader molecular weight distribution. For instance, it can be seen that catalyst compositions according to the present invention allow obtaining polypropylene with broader MWD (Ex. 1-6) compared to usual catalyst with phthalate as ID (Ex. CE1). Also, the catalysts having the internal donors comprising the N-Me bond (Ex. 1 and 4-6) or N-Et bond (Ex. 2) show broader MWD (Mw/Mn=7.1-7.8) compared to catalysts with the similar known internal donor having NH bond (Ex. CE2 and CE3, Mw/Mn=6.4-6.5). At the same time polymers obtained show high isotacticity (XS=2.5-3.6% (Ex. 1, 2, 5 and 6) compared to XS=3.5-3.6% (Ex. CE2 and CE3). It can be noted also that similar good performance of the catalysts comprising the internal donor of Formula I is observed for different magnesium-containing support-precursors (Ex. 1, 5 and 6).

(35) Abbreviations and measuring methods: PP yield, kg/g cat is the amount of polypropylene obtained per gram of catalyst component. The .sup.1H-NMR and .sup.13C-NMR spectra were recorded on a Varian Mercury-300 MHz NMR Spectrometer, using deuterated chloroform as a solvent.